Catalysis by Modified Pillared Clays and Porous Clay Heterostructures

In this venture three distinct class of catalysts such as, pillared clays and transition metal loaded pillared clays , porous clay heterostructures and their transition metal loaded analogues and DTP supported on porous clay heterostructures etc. were prepared and characterized by various physico chemical methods. The catalytic activities of prepared catalysts were comparatively evaluated for the industrially important alkylation, acetalization and oxidation reactions.The general conclusions drawn from the present investigation are  Zirconium, iron - aluminium pillared clays were synthesized by ion exchange method and zirconium-silicon porous heterostructures were Summary and conclusions 259 prepared by intergallery template method. Transition metals were loaded in PILCs and PCHs by wet impregnation method.  Textural and acidic properties of the clays were modified by pillaring and post pillaring modifications.  The shift in 2θ value to lower range and increase in d (001) spacing indicate the success of pillaring process.  Surface area, pore volume, average pore size etc. increased dramatically as a result of pillaring process.  Porous clay heterostructures have higher surface area, pore volume, average pore diameter and narrow pore size distribution than that of pillared clays.  The IR spectrum of PILCs and PCHs are in accordance with literature without much variation compared to parent montmorillonite which indicate that basic clay structure is retained even after modification.  The silicon NMR of PCHs materials have intense peaks corresponding to Q4 environment which indicate that mesoporous silica is incorporated between clay layers.  Thermo gravimetric analysis showed that thermal stability is improved after the pillaring process. PCH materials have higher thermal stability than PILCs.  In metal loaded pillared clays, up to 5% metal species were uniformly dispersed (with the exception of Ni) as evident from XRD and TPR analysis. Chapter 9 260  Impregnation of transition metals in PILCs and PCHs enhanced acidity of catalysts as evident from TPD of ammonia and cumene cracking reactions.  For porous clay heterostructures the acidic sites have major contribution from weak and medium acid sites which can be related to the Bronsted sites as evident from TPD of ammonia.  Pillared clays got more Lewis acidity than PCHs as inferred from α- methyl styrene selectivity in cumene cracking reaction.  SEM images show that layer structure is preserved even after modification. Worm hole like morphology is observed in TEM image of PCHs materials  In ZrSiPCHS, Zr exists as Zr 4+ and is incorporated to silica pillars in the intergallary of clay layers as evident from XPS analysis.  In copper loaded zirconium pillared clays, copper exists as isolated species with +2 oxidation state at lower loading. At higher loading, Cu exists as clusters as evident from reduction peak at higher temperatures in TPR.  In vanadium incorporated PILCs and PCHs, vanadium exist as isolated V5+ in tetrahedral coordination which is confirmed from TPR and UVVis DRS analysis.  In cobalt loaded PCHs, cobalt exists as CoO with 2+ oxidation state as confirmed from XPS.  Cerium incorporated iron aluminium pillared clay was found to be the best catalyst for the hydroxylation of phenol in aqueous media due to the additional surface area provided by ceria mesopores and its redox properties. Summary and conclusions 261  Cobalt loaded zirconium porous clay heterostructures were found to be promising catalyst for the tertiary butylation of phenol due to higher surface area and acidic properties.  Copper loaded pillared clays were found to be good catalyst for the direct hydroxylation of benzene to phenol.  Vanadium loaded PCHs catalysts were found to be efficient catalysts for oxidation of benzyl alcohol.  DTP was firmly fixed on the mesoporous channels of PCHs by Direct method and functionalization method.  DTP supported PCHs catalyst were found to be good catalyst for acetalization of cyclohexanone with more than 90% conversion.

Modification of Polypropylene/High Density Polyethylene Blend Using Nanokaolinite Clay and E-Glass Fibre: Preparation, Characterization and Micromechanical Modelling

Upgrading two widely used standard plastics, polypropylene (PP) and high density polyethylene (HDPE), and generating a variety of useful engineering materials based on these blends have been the main objective of this study. Upgradation was effected by using nanomodifiers and/or fibrous modifiers. PP and HDPE were selected for modification due to their attractive inherent properties and wide spectrum of use. Blending is the engineered method of producing new materials with tailor made properties. It has the advantages of both the materials. PP has high tensile and flexural strength and the HDPE acts as an impact modifier in the resultant blend. Hence an optimized blend of PP and HDPE was selected as the matrix material for upgradation. Nanokaolinite clay and E-glass fibre were chosen for modifying PP/HDPE blend. As the first stage of the work, the mechanical, thermal, morphological, rheological, dynamic mechanical and crystallization characteristics of the polymer nanocomposites prepared with PP/HDPE blend and different surface modified nanokaolinite clay were analyzed. As the second stage of the work, the effect of simultaneous inclusion of nanokaolinite clay (both N100A and N100) and short glass fibres are investigated. The presence of nanofiller has increased the properties of hybrid composites to a greater extent than micro composites. As the last stage, micromechanical modeling of both nano and hybrid A composite is carried out to analyze the behavior of the composite under load bearing conditions. These theoretical analyses indicate that the polymer-nanoclay interfacial characteristics partially converge to a state of perfect interfacial bonding (Takayanagi model) with an iso-stress (Reuss IROM) response. In the case of hybrid composites the experimental data follows the trend of Halpin-Tsai model. This implies that matrix and filler experience varying amount of strain and interfacial adhesion between filler and matrix and also between the two fillers which play a vital role in determining the modulus of the hybrid composites.A significant observation from this study is that the requirement of higher fibre loading for efficient reinforcement of polymers can be substantially reduced by the presence of nanofiller together with much lower fibre content in the composite. Hybrid composites with both nanokaolinite clay and micron sized E-glass fibre as reinforcements in PP/HDPE matrix will generate a novel class of high performance, cost effective engineering material.